Synthesis of Configurationally Defined Sexi- and Octinaphthalene Derivatives

Configurationally defined optically active octinaphthalenes were synthesized using the oxidative coupling of optically active quaternaphthalenes with a 2-hydroxynaphthol moiety as a key reaction. The absolute configuration was determined by comparison with products of [6 + 2] coupling

<i>N</i>‑Acylimino‑λ³‑iodanes from the Metathesis of Iodosoarenes and Nitriles for the Photoinduced C–H Perfluoroacylamination of (Hetero)Arenes

An efficient and scalable synthesis of N-perfluoroacylimino-λ3-iodanes was achieved via an unprecedented metathesis between iodosoarenes and perfluoroalkanenitriles. The perfluoroacylamino groups of the iodanes could be introduced to aromatic and heteroaromatic rings using photoirradiation

Functional Group Tolerance in Organocatalytic Regioselective Acylation of Carbohydrates

Organocatalytic regioselective acylation of mono- and disaccaharides with various functionalized acid anhydrides has been developed. Acylation of octyl β-d-glucopyranoside with acid anhydrides derived from α-amino acids, cinnamic acid, and gallic acid took place at C(4)-OH with 67−94% regioselectivity in the presence of catalyst 1. Regioselective acylation of disaccharides with functionalized acid anhydrides was also achieved with 78−94% selectivity. Especially, a disaccharide with seven free hydroxy groups (X = OH, R′ = H) underwent acylation at C(4)-OH with 78% regioselectivity in the presence of 1. Thus, functional group tolerance in the regioselective acylation catalyzed by 1 was found to be high

Synthetic Studies on Altemicidin: Stereocontrolled Construction of the Core Framework

The stereoselective synthesis of the key intermediate for altemicidin has been accomplished. The synthesis commenced with a bicyclo[3.3.0] framework, which was readily obtained via an intramolecular C−H insertion reaction. A Curtius rearrangement was employed as a key step to stereoselectively construct the β-hydroxyl α-disubstituted-α-amino acid structure. Synthesis of vinylogous urea was achieved using hydrolysis of nitrile intermediate

Synthetic Studies on Altemicidin: Stereocontrolled Construction of the Core Framework

The stereoselective synthesis of the key intermediate for altemicidin has been accomplished. The synthesis commenced with a bicyclo[3.3.0] framework, which was readily obtained via an intramolecular C−H insertion reaction. A Curtius rearrangement was employed as a key step to stereoselectively construct the β-hydroxyl α-disubstituted-α-amino acid structure. Synthesis of vinylogous urea was achieved using hydrolysis of nitrile intermediate

Regioselective Diversification of a Cardiac Glycoside, Lanatoside C, by Organocatalysis

Acylation of lanatoside C in the presence of organocatalyst <b>5</b> gave the C(4′′′′)-<i>O</i>-acylate in up to 90% regioselectivity (catalyst-controlled regioselectivity). Various functionalized acyl groups can be introduced at the C(4′′′′)-OH by a mixed anhydride method in the presence of <b>5</b> or the related organocatalyst. On the other hand, DMAP-catalyzed acylation of lanatoside C gave the C(3′′′′)-<i>O</i>-acylate in up to 97% regioselectivity (substrate-controlled regioselectivity). Thus, diverse regioselective introduction of acyl groups among eight free hydroxy groups of lanatoside C was achieved

Total Synthesis of (−)-Serotobenine

Total Synthesis of (−)-Serotobenin

Efficient Synthesis of Phenanthridinone Derivatives via a Palladium-Catalyzed Coupling Process^†

A palladium-mediated domino reaction was developed to conveniently synthesize phenanthridinone derivatives. Phosphine ligand 1 strongly promotes the domino process, which includes aryl−aryl coupling and C−N bond formations concomitant with a deamidation reaction. The versatility and applicability to a broad range of substrates make this reaction useful for the development of bioactive derivatives

Total Synthesis of (−)-Serotobenine

Total Synthesis of (−)-Serotobenin

Versatile Synthesis of Head Group Functionalized Phospholipids via Oxime Bond Formation

A method for introduction of various head groups on phospholipid frameworks via oxime bond formation has been developed for the synthesis of cyclen−Cu(II), pyrene, naphthalene, and other headgroup functionalized phospholipids that can cleave the membrane protein, hemagglutinin